Shale gas and groundwater quality

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Shale Gas and Groundwater Quality

A literature review on fate and effects of added chemicals

1202141-008

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1202141-008-ZWS-0001, 28 December 2011, final

1 Introduction

Shale gas is a so-called unconventional sources of natural gas, and is one of the most rapidly expanding trends in onshore domestic oil and gas exploration and production today (Fig. 1 and 2). Shale gas is present in hydrocarbon rich shale formations. Shallow gas is commonly defined as gas occurrences in unconsolidated sediments of Tertiary age (often down to depths of 1000 m below surface). The occurrences are positively associated with thick Neogene sediments and are often trapped in anticlinal structures associated with rising salt domes (Muntendam-Bos et al, 2009). Shale has low matrix permeability, so gas production in commercial quantities requires fractures to provide permeability. Hydraulic fracturing (fracking) creates extensive artificial fractures around well bores, making gas exploration possible.

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Figure 2 Detail of onconventional gas and shale gas exploration (Time, april 2011))

Shale gas has become an increasingly important source of natural gas in the United States over the past decade (Fig. 3), and interest has spread to potential gas shales in the rest of the world. It is believed that also Canada and Europe (e.g. in the Netherlands and Poland) will have large supplies of shale gas (Muntendam-Bos et al, 2009). Other advantages are the reduced CO2 emissions compared to charcoal or oil, and the independency of foreign supplies.

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Figure 3 Expected natural gas supplies in the US, including shale gas.

Europe’s dependency on natural gas is already considerable, with conventional gas accounting for 25% of the primary energy need. Half of this natural gas comes from intercontinental imports (pipeline and shipments). Off-setting the decline of Europe’s indigenous gas production from conventional fields by the development of indigenous unconventional gas fields could lower its dependency on imports from abroad. The unlocking of Europe’s unconventional gas resources therefore would increase the security of gas supply (Weijermars et al, 2011).

Shale gas development requires significant amounts of water (hydraulic fracturing) and is often conducted near valuable surface and ground water. Hydraulic fracturing is a well stimulation technique used to maximize production of oil and natural gas in unconventional reservoirs, such as shale. During hydraulic fracturing, specially engineered fluids containing chemical additives and proppant1 are pumped under high pressure into the well to create and hold open fractures in the formation. These fractures increase the exposed surface area of the rock in the formation and, in turn, stimulate the flow of natural gas or oil to the well bore. As the use of hydraulic fracturing has increased, so have concerns about its potential environmental and human health impacts. In the US, many concerns about hydraulic fracturing focus on potential risks to drinking water resources (EPA, 2011).

Questions on the impact of such activities arise, e.g. the nature of shale gas development, the potential environmental impacts, and the ability of the current regulatory structure to deal with this development.

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In the Netherlands, the British company Cuadrilla had successfully applied for a permission for a shale gas test drilling in Boxtel, in the province of Brabant. This has caused a lot of commotion in the Netherlands. In response to this public concern about announced test drillings in the Netherlands, the ministry of Economic Affairs, Agriculture and Innovation (EL&I) has announced that independent research has to be carried out before any further activities are allowed.

We have discussed shale gas exploration and possible impacts with various stakeholders, e.g. the Ministry of Infrastructure and the Environment (I&M), the Ministry of Economic Affairs Agriculture and Innovation (EL&I), DG Environment EU Brussels, Nicole (Network for Industrially Contaminated Land in Europe), TNO, KWR, RIVM, and Shell. It became obvious that stakeholders need an objective source of information on the impact of shale gas development.

During a brainstorm session on shale gas by Deltares and TNO, the following research questions were identified:

• Risk analyses, including leaking of well-casings; • Groundwater management;

• Water cycle; • Monitoring.

An integrated approach of these topics is foreseen and we have further discussed the formation of a consortium of TNO, Deltares, RIVM and KWR, to work on these topics.

This report gives a literature review on one of the environmental impacts of shale gas exploration: the effects of the chemicals used in the fracturing process. A short description of the fracturing process is given, followed by the chemicals that are used, the degradability of the chemicals, followed by a conclusion on the environmental impact of these chemicals. Shale gas exploration uses fracturing fluids of different volumes and compositions. Chapter 3 describes the numerous chemicals that are mentioned to be used in the US and Canada. Cuadrilla, the company that is planning the first bore drilling in the Netherlands, has mentioned to use only two chemicals, polyacrylamide and glutaraldehyde. Therefore, this report will be limited to those chemicals reported to be used in the Netherlands.

Other effects on groundwater quality are the release of salt, metals, methane and radioactive compounds from deeper layers. These topics are beyond the scope of the current literature review and will not be discussed in this report.

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2 The process of fracturing or fracking

Hydraulic fracturing is the propagation of fractures in a rock layer caused by the presence of a pressurized fluid, in order to release the poresent natural gas (Fig. 4). The energy from the injection of a highly-pressurized fracking fluid, creates new channels in the rock which can increase the extraction rates and ultimate recovery of the natural gas. The fracture width is typically maintained after the injection by introducing a proppant into the injected fluid. Proppant is a material, such as grains of sand, ceramic, or other particulates, that prevent the fractures from closing when the injection is stopped.

Figure 4 The process of hydraulic fracturing (EPA, 2011)

The fracturing process consists of a series of injections using different volumes and compositions of fracturing fluids (GWPC & ALL-Consulting, 2009). Sometimes a small amount of fluid is pumped into the well before the actual fracturing begins. This “mini-frac” may be used to help determine reservoir properties and to enable better fracture design (API 2009).

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In the first stage of the fracture job, fracturing fluid2 (typically without proppant) is pumped down the well at high pressures to initiate the fracture. The fracture initiation pressure will depend on the depth and the mechanical properties of the formation. A combination of fracturing fluid and proppant is then pumped into the well in varying amounts and concentrations. After the combination is pumped in, a water flush is used to begin flushing out the fracturing fluid (Arthur et al., 2008).

2_{Fracturing fluid; The fluid used during a hydraulic fracture treatment of oil, gas or water wells. The fracturing fluid has two}

major functions: (1) Open and extend the fracture, (2) Transport the proppant along the fracture length (source; Wikipedia).

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3 The use of chemicals

The make-up of fracturing fluid varies from one geologic basin or formation to another. Evaluating the relative volumes of the components of a fracturing fluid reveals the relatively small volume of additives that are present. Overall the concentration of additives in most fracturing fluids is relatively consistent, 0.5% to 2%, with water making up 98% to 99.5% (GWPC & ALL-Consulting, 2009).

In 2009, a review of chemical use in fracking operations by the New York State Department of Environmental Conservation’s Division of Mineral Resources listed 257 additives that may be mixed with the water injected into shale formations during the fracking process. They provided a breakdown of the known chemicals that stretched 10 pages long, including carcinogenic chemicals (Parfitt, 2011).

In 2011, the EPA has compiled a list of chemicals that are publicly known to be used in hydraulic fracturing (Table A). However, the chemicals in this table do not represent the entire set of chemicals used in hydraulic fracturing activities. EPA also lacks information regarding the frequency, quantity, and concentrations of the chemicals used, which is important when considering the toxic effects of hydraulic fracturing fluid additives (EPA, 2011).

In Canada, the state British Columbia does not require disclosure of the chemicals used in the fracking process. However, that may soon change, according to some remarks of the BC Premier Christy Clark, who will launch an on-line registry at the beginning of 2012 that will disclose details about hydraulic fracturing and about the additives that are used (Natural Gas Americas, 2011).

The European website www.europeunconventionalgas.org gives an overview of the chemical additives used in the fracturing process (Appendix B), such as acids, sodium, polyacrylamide, ethylene glycol, borate salts, sodium / potassium carbonate, glutaraldehyde, guar gum, citric acid and/or isopropanol, and refers to the common use of these chemicals in other products (Europe Unconventional Gas, 2011).

Cuadrilla, the company that is planning the first bore drilling in the Netherlands, has mentioned to use only two chemicals;

1 Polyacrylamide, a friction reducer, that minimizes friction between the fluid and the pipe and allows fracturing fluids and proppant to be pumped to the target zone at a higher rate and reduced pressure than if water alone were used.

2 Glutaraldehyde, a biocide that eliminates bacteria in the water that produce corrosive by-products and is added to prevent plugging of fractures due to microbial growth. In the US, the use of these two compounds in fracturing fluid are typically 0.088% friction reducers and 0.001% biocide (GWPC & ALL-Consulting, 2009). The concentration that Cuadrilla wants to use are unknown at this stage.

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4 Polyacrylamide

Polyacrylamide (PAM; Fig. 5) is a water-soluble synthetic linear polymer made of either acrylamide or a combination of acrylamide and acrylic acid.

Figure 5 Chemical structure of polyacrylamide

PAM is widely used as water purification flocculants, soil conditioning agents, anticorrosives for irrigation furrows, and in many biomedical applications. In particular, PAM is extensively used for oil production.

Polyacrylamide itself is not considered to be toxic, but is a controversial ingredient because of its potential ability to be degraded into acrylamide, a known neurotoxic.

PAM has the tendency to strongly adsorb to soil particles. As a result, a chemical extraction with solvents is needed for the quantification of the concentration in the soil. After the solvent extraction, the concentration can be measured by gas or high performance liquid chromatographic techniques. Several new techniques for the quantification of PAM adsorbed to soil, and for PAM analysis have been developed in the last years (Lu & Wu, 2003), but this might also change its molecular conformation, undermining the quantification of the concentration of the originally present concentration (Sojka et al., 2007). For quantification in the groundwater, the same methods can be used.

PAM degradation occurs slowly in soils as a result of chemical, photochemical, biological and mechanical processes (i.e., such as abrasion, freezing, thawing) because of the molecule's enormous size.

Polyacrylamide can both serve as nitrogen source, or carbon and energy source for bacteria and its degradation has been mainly described under aerobic conditions.

4.1 Aerobic degradation of polyacrylamide

Early work by MacWilliams in 1978 noted that biodegradation of polyacrylamide did not result in the formation of acrylamide and that polyacrylamide was generally very resistant to microbial degradation. Similar conclusions have also been reached by others in the eighties (Caulfield et al., 2002).

More recent, few reports in the literature exist that high molecular weight polyacrylamide can undergo biological degradation.

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Polyacrylamide as nitrogen source

Untreated and PAM-treated soils were collected from agricultural fields near Kimberly, ID. Enrichment cultures generated from PAM-treated and untreated soils utilized PAM as sole N source, but not as sole C source. This indicates that PAM may be converted into long chain polyacrylate, which may be further degraded by physical and biological mechanisms or be incorporated into organic matter (Kay-Shoemake et al., 1998).

Polyacrylamide as carbon source

In a recent study, two microorganisms (HWBI and HWBII) have been isolated which can degrade PAM. The strains were isolated from activated sludge and soil in an oil field that had been contaminated by PAM for an extended period. The cultures were identified as Bacillus

cereus and Bacillus flexu, respectively. Both strains grew on a medium with 60 mg/l PAM as

the sole source of carbon. Although both strains degraded PAM in different rates, more than 70% of the PAM was consumed after 72 h cultivation. This degradation efficiency was much higher than previous studies had ever shown (Wen et al., 2009). The result showed that amido groups of the PAM were split off by the micro-organisms from the main chain of the PAM, and metabolism products other than acrylamide were formed in the degradation.

The two enriched organisms were used to bioaugment two sequencing batch reactors (SBRs) and the performance of each strain for enhancing PAM removal was compared. The SBR augmented with HWBI showed 70% of PAM removal at each cycle. In the SBR augmented with HWBIII, only 45% of the PAM was removed in the first cycle after the inoculation, and PAM removal decreased to 30% after eight cycles (Wen et al., 2011).

Polyacrylamide as carbon and nitrogen source

Nakamiya and Kunichika have isolated from soil samples two polyacrylamide degrading bacterial strains, Enterobacter agglomerans and Azomonas macrocytogenes. Both bacterial strains grow on media containing polyacrylamide as the sole source for both carbon and nitrogen. After 27 h incubation 20% of the total organic carbon had been consumed and the average molecular weight of the polyacrylamide had been reduced from approximately 2 *106 to 0.5 * 106 (Nakamiya & Kinoshita, 1995).

Similar results were described in a later study. In diluted systems, polyacrylamide (no branched chains) degrading bacterial strains have been isolated from soil, and identified as

Bacillus sphaericus sp. and an Acinetobacter sp. Both strains grow on aerobic medium

containing polyacrylamide (10 g/l) as sole carbon and nitrogen source at 30°C. The average molecular weight of polyacrylamide has been shifted from 2.3 *106 to 0.5 * 106 (Matsuoka et

al., 2002).

Similar results were published by another Chinese research group. Two HPAM-degrading bacterial strains, named PM-2 and PM-3, were isolated from the produced water of polymer flooding. They were subsequently identified as Bacillus cereus and Bacillus sp., respectively. The amide group of HPAM could serve as a nitrogen source for the two microorganisms, the carbon backbone of these polymers could be partly utilized by micro-organisms. The amide group of HPAM in the biodegradation products had been converted to a carboxyl group, and no acrylamide monomer was found. Also the HPAM carbon backbone was metabolized by the bacteria during the course of its growth (Bao et al., 2010).

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carbon (13C/12C) and nitrogen stable isotope ratios (15N/14N), the concentration of anionic PAM in four different soils was measured, and PAM degradation rates were calculated. This resulted in an estimated PAM degradation in soil of approximately 9.8 % yr 1 (Entry et al., 2008).

4.2 Anaerobic degradation

Not much information exists on the anaerobic degradation of PAM. A sulfate reducing bacterial strain was isolated, that uses hydrolysed PAM as the only carbon source,

hydrolyzing the side chain and changing some functional groups. PAM was degraded to products of low molecular weight, but most of them were acrylamide oligomer derivatives. The removal efficiency for HPAM reached 30.8% during the 20 days cultivation (Ma et al., 2008).

Besides looking for the responsible bacteria, some studies focus on the degradation of polyacrylamide via enzymes extracted from bacteria. It was found that the lignin degrading enzyme, hydroquinone peroxidase, from the soil Azotobacter beijerinckii HM121 bacterium, was capable of degrading polyacrylamide. Extracting the enzyme and applying it to the polymer sample overcomes the limitations encountered due to the inability of high molecular weight polymer absorption into biological cells (Nakamiya et al., 1997).

4.3 Chemical or physical removal

Abiotic processes break the molecule into progressively shorter units over time. When polymer units are 6–7 monomer units long they can be degraded by soil microorganisms (Hayashi et al., 1993).

Chemical removal of PAM has been studied in aqueous solutions with ozone combined with hydrogen peroxide and ultraviolet radiation. The effects of operating parameters, including initial PAM concentration, dosages of ozone and hydrogen peroxide, UV radiation and pH value on the photochemical oxidation of PAM, have been studied. There was an increase in photochemical oxidation rate of PAM with increasing of dosages of O3, H2O2 and ultraviolet radiation. The kinetics for the photochemical oxidation of PAM by the system has been established (Ren et al., 2006), but this information is only available in Chinese.

Other chemical reactions include the hydrolysis of PAM at low pH, e.g. pH 4, or under basic or alkaline conditions at temperatures from 60-100°C.

Thermal degradation of polyacrylamide is possible, but only at temperature regions where thermal degradation primarily occurs, such as 200°C or higher.

4.4 Conclusion on removal of polyacrylamide

From the literature reviewed, the biodegradation of polyacrylamide under the influence of microbial interaction produces changes in the structure of the polymer. The amide nitrogen is susceptible to microbial degradation forming an acrylic acid residue and the release of NH3. When polyacrylamide are used as the sole carbon source for microbial growth, the degradation mainly lowers the molecular weight of the polymer, using only a part of the carbon backbone of polyacrylamide for growth. The extent of biodegradation varies, due to differences in the physical properties of the polymers studied (molecular weight, copolymers, degree of hydrolysis, history), experimental conditions, and importantly the almost infinite genetic variation that exists in nature.

No reports exist that polyacrylamide can undergo biodegradation to form free acrylamide monomer units (Caulfield et al., 2002).

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Also chemical or physical breakdown with ozone, hydrogen peroxide, ultraviolet radiation orthermal degradation is possible. Combination of this with biological degradation has not been tested, but might be an interesting option...

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5 Glutaraldehyde

Glutaraldehyde (1,5-pentanedial) (Fig. 6) is a biocide that eliminates bacteria in the water that produce corrosive byproducts and is added to prevent plugging of fractures due to microbial growth. A widely used type of glutaraldehyde is UCARCIDE™, a family of oilfield antimicrobial glutaraldehyde-based biocides, which have found widespread use in a variety of oil and gas operations (DOW, 2011).

Figure 6 Chemical structure of glutaraldehyde

Glutaraldehyde is used in many industrial applications with potential releases to the environment. Based on the results of environmental partitioning studies, glutaraldehyde shows a moderate to high potential to leach from soil (PTRL & Pharmacology and Toxicology Reseacrh Laboratory-West, 1994), and a very low tendency to enter the atmosphere from the aqueous environment due to its low air to water partition coefficient (Olson, 1998). Thus, the principal ecosystem of relevance for glutaraldehyde is the aquatic environment.

5.1 Biocide

Glutaraldehyde is a biocide and can inhibit the metabolism and growth of microbes. Such a biocide may undergo poor biodegradability if the concentration tested is inhibitory to bacteria. Results of a study in 1995 with sewage sludge showed that the EC503 was greater than 50 mg/L and the NOEC4 was 16 mg/L after 30 minutes of incubation (RCC, 1995). This suggests that concentrations of glutaraldehyde above 16 mg/L can inhibit the metabolic activity. At a longer contact time, e.g. several days, glutaraldehyde is inhibitory to microbes at a concentration above 5 mg/L (UCC, 1994).

5.2 Biodegradation

Only a few recent publications exist on the biodegradation of glutaraldehyde. A study of 2001 reports that glutaraldehyde is readily biodegradable in the freshwater environment and has the potential to biodegrade in the marine environment. Studies of glutaraldehyde in a river water–sediment system demonstrate that glutaraldehyde preferred to remain in the water phase. Glutaraldehyde was metabolized rapidly under both aerobic and anaerobic conditions, with half-life constants of 10.6 h and 7.7 h, respectively. Concentrations of 10 mg/l were tested. Under aerobic conditions, glutaraldehyde was first biotransformed into the intermediate glutaric acid, and finally to carbon dioxide. Metabolism of glutaraldehyde under anaerobic conditions did not proceed to methane, but terminated with the formation of 1,5-pentanediol via 5-hydroxypentanal as an intermediate (Leung, 2001). Higher concentrations than 10 mg/l were not tested.

The biodegradation of glutaraldehyde was studied in an aerobic laboratory-scale rotating biological contactor (RBC) with glutaraldehyde as the sole carbon source. Biofilms that were

3

EC50, half maximal effective concentration, the concentration of a compound where 50% of its maximal effect is observed.

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slowly adapted to glutaraldehyde concentration of 180 mg/L and a hydraulic retention time (HRT) of 0.6 h were grown. Removal efficiencies could be increased over time and reached 89% (Laopaiboon et al., 2008).

5.3 Chemical inactivation of glutaraldehyde

The biocide activity of glutaraldehyde is inactivated by reaction with sodium bisulfite via formation of a proposed glutaraldehyde-bisulfite complex. Neither 7.7% (0.17 M) sodium bisulfite alone nor the glutaraldehyde-bisulfite complex (50-100 ppm), was microbiocidal when tested against various bacterial strains (Jordan et al., 1996).

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6 Conclusions

This literature review shows that both chemicals polyacrylamide and glutaraldehyde can be degraded or transformed. The question is if, and how, such a removal can be applied to minimise the environmental impact of these chemicals during or after activities that are related to shale gas exploration.

For groundwater remediation, in-situ remediation is mostly preferred over on site treatment. Naturally present bacteria can be stimulated in-situ to degrade the added polyacrylamide and glutaraldehyde. Alternatively, bacteria that degrade these compounds can be added (bioaugmentation) to the contaminated groundwater.

For this, a few aspects have to be taken into account, and need further elaboration:

• When thinking of in-situ degradation processes, the infiltration depth that is used for fracking must be taking into account. As such depths, the high pressure can influence microbial processes. All described degradation processes were performed at nearly atmospheric conditions.

• The degradation of polyacrylamide is mainly effective under aerobic conditions. Such conditions are difficult to apply at the infiltration depth that is used for fracking, where the polyacrylamide might contaminate the groundwater.

• Alternatively, the groundwater is extracted and treated on site in a water treatment system. Due to the large volumes of water that are used, the scale might be complicated, and consequently, the economic feasibility is a point of concern.

• Chemical or physical breakdown of polyacrylamide is possible. The applicability and economic feasibility for contaminated ground- or surface waters will depend on the volume and concentration.

• The concentration of the used glutaraldehyde is important. Glutaraldehyde is used to prevent plugging of fractures due to microbial growth, but this also prevents the present bacteria to degrade compounds such as polyacrylamide.

• The concentrations of glutaraldehyde that will be added (0.001% ~ 10 mg/l) can be degraded by bacteria, but it is unknown if such bacteria are ubiquitously present in soil and groundwater.

• If they are ubiquitously present, is the addition of 0.001% glutaraldehyde effective or will the added glutaraldehyde be degraded without having acted as a biocide?

• If they are not ubiquitously present, the contaminated water contains an effective biocide and chemical or physical methods are needed.

Laboratory studies can help to study the combined effect of a mixture of polyacrylamide and glutaraldehyde, and are needed to better understand the ultimate fate and transport of these chemicals.

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7 References

API (American Petroleum Institute) (2009) Hydraulic fracturing operations—well construction and integrity guidelines. API Guidance Document HF1. Washington, DC: American Petroleum Institute.

Arthur JD, Bohm B & Layne M (2008) Hydraulic fracturing considerations for natural gas wells of the Marcellus Shale. Presented at The Ground Water Protection Council 2008 Annual Forum (2008, September 21-24), Cincinnati, OH.

Bao M, Chen Q, Li Y & Jiang G (2010) Biodegradation of partially hydrolyzed polyacrylamide by bacteria isolated from production water after polymer flooding in an oil field. Journal

of Hazardous Materials 184: 105-110.

Caulfield MJ, Qiao GG & Solomon DH (2002) Some aspects of the properties and degradation of polyacrylamides. Chemical Reviews 102: 3067-3084.

DOW (2011) UCARCIDE Antimicrobials for the Oilfield.

(http://msdssearch.dow.com/PublishedLiteratureDOWCOM/dh_0036/0901b8038003693 5.pdf?filepath=biocides/pdfs/noreg/253-01450.pdf.pdf&fromPage=GetDoc), p.^pp. Entry JA, Sojka RE & Hicks BJ (2008) Carbon and nitrogen stable isotope ratios can estimate

anionic polyacrylamide degradation in soil. Geoderma 145: 8-16.

EPA (Environmental Protection Agency) (2011) Plan to study the potential impacts of hydraulic fracturing on drinking water resources. EPA/600/R-11/122, 190 p. Europe Unconventional Gas (2011)

http://www.europeunconventionalgas.org/home/the-process/what-s-in-hydraulic-fracturing-fluid.

GWPC (Ground Water Protection Council) & ALL-Consulting (2009) Modern shale gas development in the US: A primer. Contract DE-FG26-04NT15455. Washington, DC: US Department of Energy, Office of Fossil Energy and National Energy Technology

Laboratory.

http://www.netl.doe.gov/technologies/oilgas/publications/EPreports/Shale_Gas_Primer_ 2009.pdf.

Hayashi T, Nashimura H, Skano K & Tani T (1993) Degradation of sodium acrylate oligomer by Athrobacter sp. Applied and Environmental Microbiology 59: 1555-1559.

Jordan SLP, Russo MR, Blessing RL & Theis AB (1996) Inactivation of glutaraldehyde by reaction with sodium bisulfite. Journal of Toxicology and Environmental Health - Part A 47: 299-309.

Kay-Shoemake JL, Watwood ME, Lentz RD & Sojka RE (1998) Polyacrylamide as an organic nitrogen source for soil microorganisms with potential effects on inorganic soil nitrogen in agricultural soil. Soil biology & biochemistry 30: 1045-1052.

Laopaiboon L, Phukoetphim N, Vichitphan K & Laopaiboon P (2008) Biodegradation of an aldehyde biocide in rotating biological contactors. World journal of microbiology &

biotechnology 24: 1633-1641.

Leung HW (2001) Aerobic and Anaerobic Metabolism of Glutaraldehyde in a River Water– Sediment System. Archives of Environmental Contamination and Toxicology 41: 267-273.

Lu JH & Wu L (2003) Polyacrylamide quantification methods in soil conservation studies. J.

Soil Water Conserv 58: 270-275.

Ma F, Wei L, Wang L & Chang C-C (2008) Isolation and identification of the

sulphate-reducing bacteria strain H1 and its function for hydrolysed polyacrylamide degradation.

International Journal of Biotechnology 10: 55-63.

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Muntendam-Bos AG, Wassing BBT, Heege JHt, van Bergen F, Schavemaker YA, van Gessel SF, de Jong ML, Nelskamp S, van Thienen-Visser K, Guasti E, . van den Belt FJG, Marges VC (2009) Inventory non-conventional gas. TNO report, nr TNO-034-UT-2009-00774/B, Utrecht, 188 p.

Nakamiya K & Kinoshita S (1995) Isolation of polyacrylamide-degrading bacteria. Journal of

Fermentation and Bioengineering 80: 418-420.

Nakamiya K, Ooi T & Kinoshita S (1997) Degradation of synthetic water-soluble polymers by hydroquinone peroxidase. Journal of Fermentation and Bioengineering 84: 213-218. Natural gas Americas, 2011, http://naturalgasforamerica.com/british-columbia.htm

Olson JD (1998) The vapor pressure of pure and aqueous glutaraldehyde. Fluid Phase

Equilibria 150-151: 713-720.

Parfitt B (2011) Fracking up our water, hydro power and climate: BC’s reckless pursuit of shale gas. 53 p.

http://www.policyalternatives.ca/sites/default/files/uploads/publications/BC%20Office/20 11/11/CCPA-BC_Fracking_Up.pdf

PTRL (Pharmacology and Toxicology Research Laboratory-West (1994) Soil adsorption / desorption of [14C]-glutaraldehyde by the batch equilibrium method, Report No. 363W-1, Pharmacology and Toxicology Research Laboratory-West, Inc., Richmond, CA.

RCC (1995) Assessment of the acute toxicity of Ucarcide] antimicrobial 250 on aerobic waste water bacteria. RCC Umweltchemie AG project 395436, Itingen, Switzerland.

Ren G-m, Sun D-z & Chung JS (2006) Kinetics study on photochemical oxidation of polyacrylamide by ozone combined with hydrogen peroxide and ultraviolet radiation.

Journal of Environmental Sciences (China) 18: 660-664.

Sojka RE, Bjorneberg DL, Entry JA, Lentz RD & Orts WJ (2007) Polyacrylamide in agriculture and environmental land management. Advances in agronomy 92: 75-162.

UCC (1994) Bacterial inhibition test results on Ucarcide Antimicrobial 250. Union Carbide Corporation, South Charleston, WV.

Weijermars R, Drijkoningen G, Heimovaara TJ, Rudolph ESJ, Weltje GJ & Wolf KHAA (2011) Unconventional gas research initiative for clean energy transition in Europe. Journal of

Natural Gas Science and Engineering 3: 402-412.

Wen Q, Chen Z, Zhao Y, Zhang H & Feng Y (2009) Biodegradation of polyacrylamide by bacteria isolated from activated sludge and oil-contaminated soil. Journal of Hazardous

Materials 175: 955-959.

Wen Q, Chen Z, Zhao Y, Zhang H & Feng Y (2011) Performance and Microbial

Characteristics of Bioaugmentation Systems for Polyacrylamide Degradation. Journal of

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Appendices

Appendix A Chemicals identified in hydraulic fracturing fluid and flowback / produced water (EPA, 2011).

Appendix B Fracturing fluid ingredients and common uses (Europe Unconventional Gas 2011).

Appendix C Properties of Polyacrylamide (source: Wikipedia) Appendix D Properties of Glutaraldehyde (source: Wikipedia)

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A Chemicals identified in hydraulic fracturing fluid and

flowback/produced water (EPA, 2011)

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EPA Hydraulic Fracturing Study Plan November 2011

A

PPENDIX

E:

C

HEMICALS

I

DENTIFIED IN

H

YDRAULIC

F

RACTURING

F

LUID AND

F

LOWBACK

/P

RODUCED

W

ATER

NOTE: In all tables in Appendix E, the chemicals are primarily listed as identified in the cited reference.

Due to varying naming conventions or errors in reporting, there may be some duplicates or inaccurate

names. Some effort has been made to eliminate errors, but further evaluation will be conducted as part

of the study analysis.

TABLE E1. CHEMICALS FOUND IN HYDRAULIC FRACTURING FLUIDS

Chemical Name Use Ref.

1-(1-naphthylmethyl)quinolinium chloride 12

1-(phenylmethyl)-ethyl pyridinium, methyl derive. Acid corrosion inhibitor 1,6,13

1,1,1-Trifluorotoluene 7

1,1':3',1''-Terphenyl 8

1,1':4',1''-Terphenyl 8

1,1-Dichloroethylene 7

1,2,3-Propanetricarboxylic acid, 2-hydroxy-, trisodium

salt, dihydrate 12,14

1,2,3-Trimethylbenzene 12, 14

1,2,4-Butanetricarboxylic acid, 2-phosphono- 12,14

1,2,4-Trimethylbenzene Non-ionic surfactant 5,10,12,13,14

1,2-Benzisothiazolin-3-one 7,12,14 1,2-Dibromo-2,4-dicyanobutane 12,14 1,2-Ethanediaminium, N, N'-bis[2-[bis(2- hydroxyethyl)methylammonio]ethyl]-N,N'bis(2-hydroxyethyl)-N,N'-dimethyl-,tetrachloride 12 1,2-Propylene glycol 8,12,14 1,2-Propylene oxide 12 1,3,5-Triazine-1,3,5(2H,4H,6H)-triethanol 12,14 1,3,5-Trimethylbenzene 12,14 1,4-Dichlorobutane 7 1,4-Dioxane 7,14

1,6 Hexanediamine Clay control 13

1,6-Hexanediamine 8,12

1,6-Hexanediamine dihydrochloride 12

1-[2-(2-Methoxy-1-methylethoxy)-1-methylethoxy]-2-propanol 13

1-3-Dimethyladamantane 8

1-Benzylquinolinium chloride Corrosion inhibitor 7,12,14

1-Butanol 7,12,14 1-Decanol 12 1-Eicosene 7,14 1-Hexadecene 7,14 1-Hexanol 12 1-Methoxy-2-propanol 7,12,14 1-Methylnaphthalene 1

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120

1-Octadecanamine, N,N-dimethyl- 12

1-Octadecene 7,14

1-Octanol 12

1-Propanaminium,

3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-coco acyl derivs., chlorides, sodium salts 12

1-Propanaminium,

3-amino-N-(carboxymethyl)-N,N-dimethyl-, N-coco acyl derivs., inner salts 7,12,14

1-Propanaminium,

N-(3-aminopropyl)-2-hydroxy-N,N-dimethyl-3-sulfo-, N-coco acyl derivs., inner salts 7,12,14

1-Propanesulfonic acid,

2-methyl-2-[(1-oxo-2-propenyl)amino]- 7,14 1-Propanol Crosslinker 10,12,14 1-Propene 13 1-Tetradecene 7,14 1-Tridecanol 12 1-Undecanol Surfactant 13

2-(2-Butoxyethoxy)ethanol Foaming agent 1

2-(2-Ethoxyethoxy)ethyl acetate 12,14 2-(Hydroxymethylamino)ethanol 12 2-(Thiocyanomethylthio)benzothiazole Biocide 13 2,2'-(Octadecylimino)diethanol 12 2,2,2-Nitrilotriethanol 8 2,2'-[Ethane-1,2-diylbis(oxy)]diethanamine 12 2,2'-Azobis-{2-(imidazlin-2-yl)propane dihydrochloride 7,14 2,2-Dibromo-3-nitrilopropionamide Biocide 1,6,7,9,10,12,14 2,2-Dibromopropanediamide 7,14 2,4,6-Tribromophenol 7 2,4-Dimethylphenol 4

2,4-Hexadienoic acid, potassium salt, (2E,4E)- 7,14

2,5 Dibromotoluene 7

2-[2-(2-Methoxyethoxy)ethoxy]ethanol 8

2-acrylamido-2-methylpropanesulphonic acid sodium

salt polymer 12

2-acrylethyl(benzyl)dimethylammonium Chloride 7,14

2-bromo-3-nitrilopropionamide Biocide 1,6

2-Butanone oxime 12

2-Butoxyacetic acid 8

2-Butoxyethanol Foaming agent, breaker

fluid 1,6,9,12,14

2-Butoxyethanol phosphate 8

2-Di-n-butylaminoethanol 12,14

2-Ethoxyethanol Foaming agent 1,6

2-Ethoxyethyl acetate Foaming agent 1

2-Ethoxynaphthalene 7,14

2-Ethyl-1-hexanol 5,12,14

2-Ethyl-2-hexenal Defoamer 13

2-Ethylhexanol 9

2-Fluorobiphenyl 7

Table continued on next page Table E1 continued from previous page

(24)

2-Fluorophenol 7

2-Hydroxyethyl acrylate 12,14

2-Mercaptoethanol 12

2-Methoxyethanol Foaming agent 1

2-Methoxyethyl acetate Foaming agent 1

2-Methyl-1-propanol Fracturing fluid 12,13,14

2-Methyl-2,4-pentanediol 12,14 2-Methyl-3(2H)-isothiazolone Biocide 12,13 2-Methyl-3-butyn-2-ol 7,14 2-Methylnaphthalene 1 2-Methylquinoline hydrochloride 7,14 2-Monobromo-3-nitrilopropionamide Biocide 10,12,14

2-Phosphonobutane-1,2,4-tricarboxylic acid, potassium

salt 12

2-Propanol, aluminum salt 12

2-Propen-1-aminium, N,N-dimethyl-N-2-propenyl-,

chloride 7,14

2-Propen-1-aminium, N,N-dimethyl-N-2-propenyl-,

chloride, homopolymer 7,14

2-Propenoic acid, polymer with sodium phosphinate 7,14

2-Propenoic acid, telomer with sodium hydrogen sulfite 7,14

2-Propoxyethanol Foaming agent 1

2-Substituted aromatic amine salt 12,14

3,5,7-Triazatricyclo(3.3.1.1(superscript 3,7))decane, 1-(3-chloro-2-propenyl)-, chloride, (Z)- 7,14 3-Bromo-1-propanol Microbiocide 1 4-(1,1-Dimethylethyl)phenol, methyloxirane, formaldehyde polymer 7,14 4-Chloro-3-methylphenol 4 4-Dodecylbenzenesulfonic acid 7,12,14

4-Ethyloct-1-yn-3-ol Acid inhibitor 5,12,14

4-Methyl-2-pentanol 12 4-Methyl-2-pentanone 5 4-Nitroquinoline-1-oxide 7 4-Terphenyl-d14 7 (4R)-1-methyl-4-(prop-1-en-2-yl)cyclohexene 5,12,14 5-Chloro-2-methyl-3(2H)-isothiazolone Biocide 12,13,14 6-Methylquinoline 8 Acetaldehyde 12,14

Acetic acid Acid treatment, buffer 5,6,9,10,12,14

Acetic acid, cobalt(2+) salt 12,14

Acetic acid, hydroxy-, reaction products with

triethanolamine 14

Acetic anhydride 5,9,12,14

Acetone Corrosion Inhibitor 5,6,12,14

Acetonitrile, 2,2',2''-nitrilotris- 12

Acetophenone 12

(25)

122

Acetylene 9 Acetylenic alcohol 12 Acetyltriethyl citrate 12 Acrolein Biocide 13 Acrylamide 7,12,14 Acrylamide copolymer 12

Acrylamide-sodium acrylate copolymer 7,14

Acrylamide-sodium-2-acrylamido-2-methlypropane

sulfonate copolymer Gelling agent 7,12,14

Acrylate copolymer 12

Acrylic acid/2-acrylamido-methylpropylsulfonic acid

copolymer 12

Acrylic copolymer 12

Acrylic polymers 12,14

Acrylic resin 14

Acyclic hydrocarbon blend 12

Adamantane 8

Adipic acid Linear gel polymer 6,12,14

Alcohol alkoxylate 12

Alcohols 12,14

Alcohols, C11-14-iso-, C13-rich 7,14

Alcohols, C9-C22 12

Alcohols; C12-14-secondary 12,14

Aldehyde Corrosion inhibitor 10,12,14

Aldol 12,14

Alfa-alumina 12,14

Aliphatic acids 7,12,14

Aliphatic alcohol glycol ether 14

Aliphatic alcohol polyglycol ether 12

Aliphatic amine derivative 12

Aliphatic hydrocarbon (naphthalenesulfonic acide,

sodium salt, isopropylated) Surfactant 13

Alkaline bromide salts 12

Alkalinity 13 Alkanes, C10-14 12 Alkanes, C1-2 4 Alkanes, C12-14-iso- 14 Alkanes, C13-16-iso- 12 Alkanes, C2-3 4 Alkanes, C3-4 4 Alkanes, C4-5 4 Alkanolamine/aldehyde condensate 12 Alkenes 12 Alkenes, C>10 .alpha.- 7,12,14 Alkenes, C>8 12 Alkoxylated alcohols 12 Alkoxylated amines 12

Alkoxylated phenol formaldehyde resin 12,14

(26)

Alkyaryl sulfonate 12

Alkyl alkoxylate 12,14

Alkyl amine 12

Alkyl amine blend in a metal salt solution 12,14

Alkyl aryl amine sulfonate 12

Alkyl aryl polyethoxy ethanol 7,14

Alkyl esters 12,14

Alkyl hexanol 12,14

Alkyl ortho phosphate ester 12

Alkyl phosphate ester 12

Alkyl quaternary ammonium chlorides 12

Alkyl* dimethyl benzyl ammonium chloride

*(61% C12, 23% C14, 11% C16, 2.5% C18 2.5% C10 and trace of C8) Corrosion inhibitor 7

Alkylaryl sulfonate 7,12,14

Alkylaryl sulphonic acid 12

Alkylated quaternary chloride 12,14

Alkylbenzenesulfonate, linear Foaming agent 5,6,12

Alkylbenzenesulfonic acid 9,12,14

Alkylethoammonium sulfates 12

Alkylphenol ethoxylates 12

Almandite and pyrope garnet 12,14

Alpha-C11-15-sec-alkyl-omega-hydroxypoly(oxy-1,2-ethanediyl) 12 Alpha-Terpineol 8 Alumina Proppant 12,13,14 Aluminium chloride 7,12,14 Aluminum Crosslinker 4,6,12,14 Aluminum oxide 12,14

Aluminum oxide silicate 12

Aluminum silicate Proppant 13,14

Aluminum sulfate 12,14

Amides, coco, N-[3-(dimethylamino)propyl] 12,14

Amides, coco, N-[3-(dimethylamino)propyl], alkylation

products with chloroacetic acid, sodium salts 12

Amides, coco, N-[3-(dimethylamino)propyl], N-oxides 7,12,14

Amides, tall-oil fatty, N,N-bis(hydroxyethyl) 7,14

Amides, tallow, n-[3-(dimethylamino)propyl],n-oxides 12

Amidoamine 12 Amine 12,14 Amine bisulfite 12 Amine oxides 12 Amine phosphonate 12 Amine salt 12

Amines, C14-18; C16-18-unsaturated, alkyl, ethoxylated 12

Amines, C8-18 and C18-unsatd. alkyl Foaming agent 5

Amines, coco alkyl, acetate 12

Amines, coco alkyl, ethoxylated 14

(27)

124

Amines, polyethylenepoly-, ethoxylated,

phosphonomethylated 12

Amines, tallow alkyl, ethoxylated, acetates (salts) 12,14

Amino compounds 12

Amino methylene phosphonic acid salt 12

Aminotrimethylene phosphonic acid 12

Ammonia 9,11,12,14

Ammonium acetate Buffer 5,10,12,14

Ammonium alcohol ether sulfate 7,12,14

Ammonium bifluoride 9

Ammonium bisulfite Oxygen scavenger 3,9,12,14

Ammonium C6-C10 alcohol ethoxysulfate 12

Ammonium C8-C10 alkyl ether sulfate 12

Ammonium chloride Crosslinker 1,6,10,12,14

Ammonium citrate 7,14

Ammonium fluoride 12,14

Ammonium hydrogen carbonate 12,14

Ammonium hydrogen difluoride 12,14

Ammonium hydrogen phosphonate 14

Ammonium hydroxide 7,12,14

Ammonium nitrate 7,12,14

Ammonium persulfate Breaker fluid 1,6,9

Ammonium salt 12,14

Ammonium salt of ethoxylated alcohol sulfate 12,14

Ammonium sulfate Breaker fluid 5,6,12,14

Amorphous silica 9,12,14

Anionic copolymer 12,14

Anionic polyacrylamide 12,14

Anionic polyacrylamide copolymer Friction reducer 5,6,12

Anionic polymer 12,14

Anionic polymer in solution 12

Anionic surfactants Friction reducer 5,6

Anionic water-soluble polymer 12

Anthracene 4

Antifoulant 12

Antimonate salt 12,14

Antimony 7

Antimony pentoxide 12

Antimony potassium oxide 12,14

Antimony trichloride 12

Aromatic alcohol glycol ether 12

Aromatic aldehyde 12

Aromatic hydrocarbons 13,14

Aromatic ketones 12,14

Aromatic polyglycol ether 12

Aromatics 1

Arsenic 4

Arsenic compounds 14

(28)

Ashes, residues 14

Atrazine 8

Attapulgite Gelling agent 13

Barium 4

Barium sulfate 5,12,14

Bauxite Proppant 12,13,14

Bentazone 8

Bentone clay 14

Bentonite Fluid additives 5,6,12,14

Bentonite, benzyl(hydrogenated tallow alkyl)

dimethylammonium stearate complex 14

Benzalkonium chloride 14

Benzene Gelling agent 1,12,14

Benzene, 1,1'-oxybis-, tetrapropylene derivs.,

sulfonated, sodium salts 14

Benzene, C10-16-alkyl derivs. 12

Benzenesulfonic acid, (1-methylethyl)-, ammonium salt 7,14

Benzenesulfonic acid, C10-16-alkyl derivs. 12,14

Benzenesulfonic acid, C10-16-alkyl derivs., potassium

salts 12,14 Benzo(a)pyrene 4 Benzoic acid 9,12,14 Benzyl chloride 12 Benzyl-dimethyl-(2-prop-2-enoyloxyethyl)ammonium chloride 8 Benzylsuccinic acid 8 Beryllium 11 Bicarbonate 7 Bicine 12 Biocide component 12 Bis(1-methylethyl)naphthalenesulfonic acid, cyclohexylamine salt 12

Bis(2-methoxyethyl) ether Foaming Agent 1

Bishexamethylenetriamine penta methylene

phosphonic acid 12

Bisphenol A 8

Bisphenol A/Epichlorohydrin resin 12,14

Bisphenol A/Novolac epoxy resin 12,14

Blast furnace slag Viscosifier 13,14

Borate salts Crosslinker 3,12,14

Borax Crosslinker 1,6,12,14

Boric acid Crosslinker 1,6,9,12,14

Boric acid, potassium salt 12,14

Boric acid, sodium salt 9,12

Boric oxide 7,12,14

Boron 4

Boron sodium oxide 12,14

Boron sodium oxide tetrahydrate 12,14

(29)

126

Bromide (-1) 7

Bromodichloromethane 7

Bromoform 7

Bronopol Microbiocide 5,6,12,14

Butane 5

Butanedioic acid, sulfo-, 1,4-bis(1,3-dimethylbutyl)

ester, sodium salt 12

Butyl glycidyl ether 12,14

Butyl lactate 12,14

C.I. Pigment orange 5 14

C10-C16 ethoxylated alcohol Surfactant 12,13,14

C-11 to C-14 n-alkanes, mixed 12

C12-14-tert-alkyl ethoxylated amines 7,14

Cadmium 4 Cadmium compounds 13,14 Calcium 4 Calcium bromide 14 Calcium carbonate 12,14 Calcium chloride 7,9,12,14

Calcium dichloride dihydrate 12,14

Calcium fluoride 12

Calcium hydroxide pH control 12,13,14

Calcium hypochlorite 12,14

Calcium oxide Proppant 9,12,13,14

Calcium peroxide 12

Calcium sulfate Gellant 13,14

Carbohydrates 5,12,14

Carbon 14

Carbon black Resin 13,14

Carbon dioxide Foaming agent 5,6,12,14

Carbonate alkalinity 7

Carbonic acid calcium salt (1:1) pH control 12,13

Carbonic acid, dipotassium salt 12,14

Carboxymethyl cellulose 8

Carboxymethyl guar gum, sodium salt 12

Carboxymethyl hydroxypropyl guar 9,12,14

Carboxymethylguar Linear gel polymer 6

Carboxymethylhydroxypropylguar Linear gel polymer 6

Cationic polymer Friction reducer 5,6

Caustic soda 13,14

Caustic soda beads 13,14

Cellophane 12,14

Cellulase enzyme 12

Cellulose 7,12,14

Cellulose derivative 12,14

Ceramic 13,14

Cetyl trimethyl ammonium bromide 12

CFR-3 14

(30)

Chloride 4 Chloride (-1) 14 Chlorine Lubricant 13 Chlorine dioxide 7,12,14 Chlorobenzene 4 Chlorodibromomethane 7 Chloromethane 7

Chlorous ion solution 12

Choline chloride 9,12,14

Chromates 12,14

Chromium Crosslinker 11

Chromium (III) acetate 12

Chromium (III), insoluble salts 6

Chromium (VI) 6

Chromium acetate, basic 13

Cinnamaldehyde (3-phenyl-2-propenal) 9,12,14

Citric acid Iron control 3,9,12,14

Citrus terpenes 7,12,14

Coal, granular 12,14

Cobalt 7

Coco-betaine 7,14

Coconut oil acid/diethanolamine condensate (2:1) 12

Collagen (gelatin) 12,14

Common White 14

Complex alkylaryl polyo-ester 12

Complex aluminum salt 12

Complex organometallic salt 12

Complex polyamine salt 9

Complex substituted keto-amine 12

Complex substituted keto-amine hydrochloride 12

Copolymer of acrylamide and sodium acrylate 12,14

Copper 5,12

Copper compounds Breaker fluid 1,6

Copper sulfate 7,12,14

Copper(I) iodide Breaker fluid 5,6,12,14

Copper(II) chloride 7,12,14

Coric oxide 14

Corn sugar gum Corrosion inhibitor 12,13,14

Corundum 14 Cottonseed flour 13,14 Cremophor(R) EL 7,12,14 Crissanol A-55 7,14 Cristobalite 12,14 Crotonaldehyde 12,14

Crystalline silica, tridymite 12,14

Cumene 7,12,14

Cupric chloride dihydrate 7,9,12

Cuprous chloride 12,14

(31)

128

Cured acrylic resin 12,14

Cured resin 9,12,14

Cured silicone rubber-polydimethylsiloxane 12

Cured urethane resin 12,14

Cyanide 11 Cyanide, free 7 Cyclic alkanes 12 Cyclohexane 9,12 Cyclohexanone 12,14 D-(-)-Lactic acid 12,14 Dapsone 12,14 Dazomet Biocide 9,12,13,14 Decyldimethyl amine 7,14 D-Glucitol 7,12,14 D-Gluconic acid 12 D-Glucose 12 D-Limonene 5,7,9 Di(2-ethylhexyl) phthalate 7,12

Diatomaceous earth, calcined 12

Diatomaceus earth Proppant 13,14

Dibromoacetonitrile 7,12,14

Dibutyl phthalate 4

Dicalcium silicate 12,14

Dicarboxylic acid 12

Didecyl dimethyl ammonium chloride Biocide 12,13

Diesel 1,6,12

Diethanolamine Foaming agent 1,6,12,14

Diethylbenzene 7,12,14

Diethylene glycol 5,9,12,14

Diethylene glycol monobutyl ether 8

Diethylene glycol monoethyl ether Foaming agent 1

Diethylene glycol monomethyl ether Foaming agent 1,12,14

Diethylenetriamine Activator 10,12,14 Diisopropylnaphthalene 7,14 Diisopropylnaphthalenesulfonic acid 7,12,14 Dimethyl glutarate 12,14 Dimethyl silicone 12,14 Dinonylphenyl polyoxyethylene 14

Dipotassium monohydrogen phosphate 5

Dipropylene glycol 7,12,14

Di-secondary-butylphenol 12

Disodium

dodecyl(sulphonatophenoxy)benzenesulphonate 12

Disodium ethylenediaminediacetate 12

Disodium ethylenediaminetetraacetate dihydrate 12

Dispersing agent 12

Distillates, petroleum, catalytic reformer fractionator

residue, low-boiling 12

(32)

Distillates, petroleum, hydrodesulfurized light catalytic

cracked 12

Distillates, petroleum, hydrodesulfurized middle 12

Distillates, petroleum, hydrotreated heavy naphthenic 5,12,14

Distillates, petroleum, hydrotreated heavy paraffinic 12,14

Distillates, petroleum, hydrotreated light Friction reducer 5,9,10,12,14

Distillates, petroleum, hydrotreated light naphthenic 12

Distillates, petroleum, hydrotreated middle 12

Distillates, petroleum, light catalytic cracked 12

Distillates, petroleum, solvent-dewaxed heavy paraffinic 12,14

Distillates, petroleum, solvent-refined heavy naphthenic 12

Distillates, petroleum, steam-cracked 12

Distillates, petroleum, straight-run middle 12,14

Distillates, petroleum, sweetened middle 12,14

Ditallow alkyl ethoxylated amines 7,14

Docusate sodium 12

Dodecyl alcohol ammonium sulfate 12

Dodecylbenzene 7,14

Dodecylbenzene sulfonic acid salts 12,14

Dodecylbenzenesulfonate isopropanolamine 7,12,14

Dodecylbenzene sulfonic acid, monoethanolamine salt 12

Dodecylbenzene sulphonic acid, morpholine salt 12,14

Econolite Additive 14

Edifas B Fluid additives 5,14

EDTA copper chelate Breaker fluid, activator 5,6,10,12,14

Endo- 1,4-beta-mannanase, or Hemicellulase 14

EO-C7-9-iso; C8 rich alcohols 14

EO-C9-11-iso; C10 rich alcohols 12,14

Epichlorohydrin 12,14

Epoxy resin 12

Erucic amidopropyl dimethyl detaine 7,12,14

Essential oils 12

Ester salt Foaming agent 1

Ethanaminium,

N,N,N-trimethyl-2-[(1-oxo-2-propenyl)oxy]-, chloride 14

Ethanaminium,

N,N,N-trimethyl-2-[(1-oxo-2-propenyl)oxy]-,chloride, polymer with 2-propenamide 12,14

Ethane 5

Ethanol Foaming agent,

non-ionic surfactant 1,6,10,12,14

Ethanol, 2,2'-iminobis-, N-coco alkyl derivs., N-oxides 12

Ethanol, 2,2'-iminobis-, N-tallow alkyl derivs. 12

Ethanol, 2-[2-[2-(tridecyloxy)ethoxy]ethoxy]-, hydrogen

sulfate, sodium salt 12

Ethanolamine Crosslinker 1,6,12,14

Ethoxylated 4-nonylphenol 13

(33)

130

Ethoxylated alcohol/ester mixture 14

Ethoxylated alcohols16 5,9,12,13,14

Ethoxylated alkyl amines 12,14

Ethoxylated amine 12,14

Ethoxylated fatty acid ester 12,14

Ethoxylated fatty acid, coco 14

Ethoxylated fatty acid, coco, reaction product with

ethanolamine 14

Ethoxylated nonionic surfactant 12

Ethoxylated nonylphenol 8,12,14

Ethoxylated propoxylated C12-14 alcohols 12,14

Ethoxylated sorbitan trioleate 7,14

Ethoxylated sorbitol esters 12,14

Ethoxylated undecyl alcohol 12

Ethoxylated, propoxylated trimethylolpropane 7,14

Ethylacetate 9,12,14

Ethylacetoacetate 12

Ethyllactate 7,14

Ethylbenzene Gelling Agent 1,9,12,14

Ethylcellulose Fluid Additives 13

Ethylene glycol Crosslinker/ Breaker

Fluids/ Scale Inhibitor 1,6,9,12,14

Ethylene glycol diethyl ether Foaming Agent 1

Ethylene glycol dimethyl ether Foaming Agent 1

Ethylene oxide 7,12,14

Ethylene oxide-nonylphenol polymer 12

Ethylenediaminetetraacetic acid 12,14

Ethylenediaminetetraacetic acid tetrasodium salt

hydrate 7,12,14

Ethylenediaminetetraacetic acid, diammonium copper

salt 14

Ethylene-vinyl acetate copolymer 12

Ethylhexanol 14

Fatty acid ester 12

Fatty acid, tall oil, hexa esters with sorbitol, ethoxylated 12,14

Fatty acids 12

Fatty acids, tall oil reaction products w/acetophenone,

formaldehyde & thiourea 14

Fatty acids, tall-oil 7,12,14

Fatty acids, tall-oil, reaction products with

diethylenetriamine 12

Fatty acids, tallow, sodium salts 7,14

Fatty alcohol alkoxylate 12,14

Fatty alkyl amine salt 12

Table continued on next page

16

Multiple categories of ethoxylated alcohols were listed in various references. Due to different naming conventions, there is some uncertainty as to whether some are duplicates or some incorrect. Therefore, “ethoxylated alcohols” is included here as a single item with further evaluation to follow.

(34)

Fatty amine carboxylates 12

Fatty quaternary ammonium chloride 12

FD & C blue no. 1 12

Ferric chloride 7,12,14

Ferric sulfate 12,14

Fluorene 1

Fluoride 7

Fluoroaliphatic polymeric esters 12,14

Formaldehyde polymer 12

Formaldehyde, polymer with 4-(1,1-dimethyl)phenol,

methyloxirane and oxirane 12

Formaldehyde, polymer with 4-nonylphenol and

oxirane 12

Formaldehyde, polymer with ammonia and phenol 12

Formaldehyde, polymers with branched 4-nonylphenol,

ethylene oxide and propylene oxide 14

Formalin 7,12,14

Formamide 7,12,14

Formic acid Acid Treatment 1,6,9,12,14

Formic acid, potassium salt 7,12,14

Fuel oil, no. 2 12,14

Fuller’s earth Gelling agent 13

Fumaric acid Water gelling agent/

linear gel polymer 1,6,12,14

Furfural 12,14

Furfuryl alcohol 12,14

Galactomannan Gelling agent 13

Gas oils, petroleum, straight-run 12

Gilsonite Viscosifier 12,14

Glass fiber 7,12,14

Gluconic acid 9

Glutaraldehyde Biocide 3,9,12,14

Glycerin, natural Crosslinker 7,10,12,14

Glycine, N-(carboxymethyl)-N-(2-hydroxyethyl)-,

disodium salt 12

Glycine, N,N'-1,2-ethanediylbis[N-(carboxymethyl)-,

disodium salt 7,12,14

Glycine, N,N-bis(carboxymethyl)-, trisodium salt 7,12,14

Glycine,

N-[2-[bis(carboxymethyl)amino]ethyl]-N-(2-hydroxyethyl)-, trisodium salt 12

Glycol ethers 9,12

Glycolic acid 7,12,14

Glycolic acid sodium salt 7,12,14

Glyoxal 12

Glyoxylic acid 12

Graphite Fluid additives 13

Guar gum 9,12,14

Guar gum derivative 12

(35)

132

Gypsum 13,14

Haloalkyl heteropolycycle salt 12

Heavy aromatic distillate 12

Heavy aromatic petroleum naphtha 13,14

Hematite 12,14

Hemicellulase 5,12,14

Heptane 5,12

Heptene, hydroformylation products, high-boiling 12

Hexane 5

Hexanes 12

Hydrated aluminum silicate 12,14

Hydrocarbons 12

Hydrocarbons, terpene processing by-products 7,12,14

Hydrochloric acid Acid treatment, solvent 1,6,9,10,12,14

Hydrogen fluoride (Hydrofluoric acid) Acid treatment 12

Hydrogen peroxide 7,12,14

Hydrogen sulfide 7,12

Hydrotreated and hydrocracked base oil 12

Hydrotreated heavy naphthalene 5

Hydrotreated light distillate 14

Hydrotreated light petroleum distillate 14

Hydroxyacetic acid ammonium salt 7,14

Hydroxycellulose Linear gel polymer 6

Hydroxyethylcellulose Gel 3,12,14

Hydroxylamine hydrochloride 7,12,14

Hydroxyproplyguar Linear gel polymer 6

Hydroxypropyl cellulose 8

Hydroxypropyl guar gum Linear gel delivery,

water gelling agent 1,6,10,12,14

Hydroxysultaine 12

Igepal CO-210 7,12,14

Inner salt of alkyl amines 12,14

Inorganic borate 12,14

Inorganic particulate 12,14

Inorganic salt 12

Instant coffee purchased off the shelf 12

Inulin, carboxymethyl ether, sodium salt 12

Iron Emulsifier/surfactant 13

Iron oxide Proppant 12,13,14

Iron(II) sulfate heptahydrate 7,12,14

Iso-alkanes/n-alkanes 12,14

Isoascorbic acid 7,12,14

Isomeric aromatic ammonium salt 7,12,14

Isooctanol 5,12,14

Isooctyl alcohol 12

Isopentyl alcohol 12

(36)

Isopropanol Foaming agent/

surfactant, acid corrosion inhibitor

1,6,9,12,14

Isopropylamine 12

Isoquinoline, reaction products with benzyl chloride and

quinoline 14

Isotridecanol, ethoxylated 7,12,14

Kerosine, petroleum, hydrodesulfurized 7,12,14

Kyanite Proppant 12,13,14 Lactic acid 12 Lactose 7,14 Latex 2000 13,14 L-Dilactide 12,14 Lead 4,12 Lead compounds 14

Lignite Fluid additives 13

Lime 14

Lithium 7

L-Lactic acid 12

Low toxicity base oils 12

Lubra-Beads coarse 14

Maghemite 12,14

Magnesium 4

Magnesium aluminum silicate Gellant 13

Magnesium carbonate 12

Magnesium chloride Biocide 12,13

Magnesium chloride hexahydrate 14

Magnesium hydroxide 12

Magnesium iron silicate 12,14

Magnesium nitrate Biocide 12,13,14

Magnesium oxide 12,14 Magnesium peroxide 12 Magnesium phosphide 12 Magnesium silicate 12,14 Magnetite 12,14 Manganese 4 Mercury 11 Metal salt 12

Metal salt solution 12

Methanamine, N,N-dimethyl-, hydrochloride 5,12,14

Methane 5

Methanol Acid corrosion inhibitor 1,6,9,10,12,14

Methenamine 12,14

Methyl bromide 7

Methyl ethyl ketone 4

Methyl salicylate 9

Methyl tert-butyl ether Gelling agent 1

Methyl vinyl ketone 12

(37)

134

Methylcyclohexane 12

Methylene bis(thiocyanate) Biocide 13

Methyloxirane polymer with oxirane, mono

(nonylphenol) ether, branched 14

Mica Fluid additives 5,6,12,14

Microbond expanding additive 14

Mineral 12,14

Mineral filler 12

Mineral oil Friction reducer 3,14

Mixed titanium ortho ester complexes 12

Modified lignosulfonate 14

Modified alkane 12,14

Modified cycloaliphatic amine adduct 12,14

Modified lignosulfonate 12

Modified polysaccharide or pregelatinized cornstarch or

starch 8 Molybdenum 7 Monoethanolamine 14 Monoethanolamine borate 12,14 Morpholine 12,14 Muconic acid 8 Mullite 12,14 N,N,N-Trimethyl-2[1-oxo-2-propenyl]oxy ethanaminimum chloride 7,14 N,N,N-Trimethyloctadecan-1-aminium chloride 12 N,N'-Dibutylthiourea 12

N,N-Dimethyl formamide Breaker 3,14

N,N-Dimethyl-1-octadecanamine-HCl 12 N,N-Dimethyldecylamine oxide 7,12,14 N,N-Dimethyldodecylamine-N-oxide 8 N,N-Dimethylformamide 5,12,14 N,N-Dimethyl-methanamine-n-oxide 7,14 N,N-Dimethyl-N-[2-[(1-oxo-2-propenyl)oxy]ethyl]-benzenemethanaminium chloride 7,14 N,N-Dimethyloctadecylamine hydrochloride 12 N,N'-Methylenebisacrylamide 12,14 n-Alkanes,C10-C18 4 n-Alkanes,C18-C70 4 n-Alkanes,C5-C8 4 n-Butanol 9

Naphtha, petroleum, heavy catalytic reformed 5,12,14

Naphtha, petroleum, hydrotreated heavy 7,12,14

Naphthalene Gelling agent, non-ionic

surfactant 1,9,10,12,14

Naphthalene derivatives 12

Naphthalenesulphonic acid, bis (1-methylethyl)-methyl

derivatives 12

Naphthenic acid ethoxylate 14

(38)

Navy fuels JP-5 7,12,14

Nickel 4

Nickel sulfate Corrosion inhibitor 13

Nickel(II) sulfate hexahydrate 12

Nitrazepam 8

Nitrilotriacetamide scale inhibiter 9,12

Nitrilotriacetic acid 12,14

Nitrilotriacetic acid trisodium monohydrate 12

Nitrobenzene 8

Nitrobenzene-d5 7

Nitrogen, liquid Foaming agent 5,6,12,14

N-Lauryl-2-pyrrolidone 12

N-Methyl-2-pyrrolidone 12,14

N-Methyldiethanolamine 8

N-Oleyl diethanolamide 12

Nonane, all isomers 12

Non-hazardous salt 12

Nonionic surfactant 12

Nonylphenol (mixed) 12

Nonylphenol ethoxylate 8,12,14

Nonylphenol, ethoxylated and sulfated 12

N-Propyl zirconate 12

N-Tallowalkyltrimethylenediamines 12,14

Nuisance particulates 12

Nylon fibers 12,14

Oil and grease 4

Oil of wintergreen 12,14

Oils, pine 12,14

Olefinic sulfonate 12

Olefins 12

Organic acid salt 12,14

Organic acids 12

Organic phosphonate 12

Organic phosphonate salts 12

Organic phosphonic acid salts 12

Organic salt 12,14

Organic sulfur compound 12

Organic surfactants 12

Organic titanate 12,14

Organo-metallic ammonium complex 12

Organophilic clays 7,12,14

O-Terphenyl 7,14

Other inorganic compounds 12

Oxirane, methyl-, polymer with oxirane,

mono-C10-16-alkyl ethers, phosphates 12

Oxiranemethanaminium, N,N,N-trimethyl-, chloride,

homopolymer 7,14

Oxyalkylated alcohol 12,14

(39)

136

Oxyalkylated alkyl alcohol 12

Oxyalkylated alkylphenol 7,12,14

Oxyalkylated fatty acid 12

Oxyalkylated phenol 12

Oxyalkylated polyamine 12

Oxylated alcohol 5,12,14

P/F resin 14

Paraffin waxes and hydrocarbon waxes 12

Paraffinic naphthenic solvent 12

Paraffinic solvent 12,14

Paraffins 12

Pentaerythritol 8

Pentane 5

Perlite 14

Peroxydisulfuric acid, diammonium salt Breaker fluid 1,6,12,14

Petroleum 12

Petroleum distillates 12,14

Petroleum gas oils 12

Petroleum hydrocarbons 7

Phenanthrene Biocide 1,6

Phenol 4,12,14

Phenolic resin Proppant 9,12,13,14

Phosphate ester 12,14

Phosphate esters of alkyl phenyl ethoxylate 12

Phosphine 12,14

Phosphonic acid 12

Phosphonic acid (dimethlamino(methylene)) 12

Phosphonic acid, (1-hydroxyethylidene)bis-,

tetrasodium salt 12,14

Phosphonic acid,

[[(phosphonomethyl)imino]bis[2,1-ethanediylnitrilobis(methylene)]]tetrakis- Scale inhibitor 12,13 Phosphonic acid,

[[(phosphonomethyl)imino]bis[2,1-ethanediylnitrilobis(methylene)]]tetrakis-, sodium salt 7,14

Phosphonic acid, [nitrilotris(methylene)]tris-,

pentasodium salt 12

[[(Phosphonomethyl)imino]bis[2,1-ethanediylnitrilobis(methylene)]]tetrakis phosphonic acid ammonium salt

7,14

Phosphoric acid ammonium salt 12

Phosphoric acid Divosan X-Tend formulation 12

Phosphoric acid, aluminium sodium salt Fluid additives 12,13

Phosphoric acid, diammonium salt Corrosion inhibitor 13

Phosphoric acid, mixed decyl and Et and octyl esters 12

Phosphoric acid, monoammonium salt 14

Phosphorous acid 12

Phosphorus 7

Phthalic anhydride 12

Plasticizer 12

(40)

Pluronic F-127 12,14

Poly (acrylamide-co-acrylic acid), partial sodium salt 14

Poly(oxy-1,2-ethanediyl), .alpha.-(nonylphenyl)-omega-hydroxy-, phosphate 12,14 Poly(oxy-1,2-ethanediyl), .alpha.-(octylphenyl)-omega-hydroxy-, branched 12 Poly(oxy-1,2-ethanediyl), alpha,alpha'-[[(9Z)-9- octadecenylimino]di-2,1-ethanediyl]bis[.omega.-hydroxy- 12,14 Poly(oxy-1,2-ethanediyl), alpha-sulfo-.omega.-hydroxy-,

C12-14-alkyl ethers, sodium salts 12,14

Poly(oxy-1,2-ethanediyl), alpha-hydro-omega-hydroxy 12 Poly(oxy-1,2-ethanediyl), alpha-sulfo-omega-(hexyloxy)-ammonium salt 12,14 Poly(oxy-1,2-ethanediyl), alpha-tridecyl-omega-hydroxy- 12,14 Poly-(oxy-1,2-ethanediyl)-alpha-undecyl-omega-hydroxy 12,14

Poly(oxy-1,2-ethanediyl)-nonylphenyl-hydroxy Acid corrosion inhibitor, non-ionic surfactant 7,12,13,14 Poly(sodium-p-styrenesulfonate) 12 Poly(vinyl alcohol) 12 Poly[imino(1,6-dioxo-1,6-hexanediyl)imino-1,6-hexanediyl] Resin 13

Polyacrylamide Friction reducer 3,6,12,13,14

Polyacrylamides 12

Polyacrylate 12,14

Polyamine 12,14

Polyamine polymer 14

Polyanionic cellulose 12

Polyaromatic hydrocarbons Gelling agent/

bactericides 1,6,13

Polycyclic organic matter Gelling agent/

bactericides 1,6,13

Polyethene glycol oleate ester 7,14

Polyetheramine 12

Polyethoxylated alkanol 7,14

Polyethylene glycol 5,9,12,14

Polyethylene glycol ester with tall oil fatty acid 12

Polyethylene glycol

mono(1,1,3,3-tetramethylbutyl)phenyl ether 7,12,14

Polyethylene glycol monobutyl ether 12,14

Polyethylene glycol nonylphenyl ether 7,12,14

Polyethylene glycol tridecyl ether phosphate 12

Polyethylene polyammonium salt 12

Polyethyleneimine 14

Polyglycol ether Foaming agent 1,6,13

Shale gas and groundwater quality